Manufacture of artificial threads and other products from cellulose compounds



Patented June 11, 1935 MANUFACTURE OF ARTIFICIAL THREADS AND OTHER PRODUCTS FROM CELLULOSE COMPOUNDS Leon Lilieniteld, Vienna, Austria Nb, Drawing. Application July 14, 1933, Serial No. 680,499. In Great Britain July 15, 1932 7 Claims.

In certain of my copending cases, as noted below, I have shown, described and claimed processes of producing artificial materials (e. g. threads, films, coatings or dressings on. textiles,

6 paper, etc., and numerous others) by forming what may ,be consideredtobe a solutionof a xanthate of a cellulosic body in which. one or more .of the hydroxyl'hydrogen atoms has been replaced by organic radicals, and then coagulat- 10 ingthe latter in a shaped condition either by treating with a plasticizingbath (e. g. H2804 of at least 35% and preferably 45% or stronger,

or other acid bath having a similar, strength) or by coagulating said xanthate solution, in a shaped condition, with an acid having merely a coagulating action (e. g. a more dilute H2804 solution or other acid solution or acid salt solution or acid and salt solution) and, if desired, then treating thev freshly .coagulated artificial material with a plasticizing bath (as set forth above).

There aretwo general methods of preparing the solution of xanthates of oxy-organo compounds of cellulose (which term will be hereinafter used to designate the saidxanthate solution, -forthe sake of brevity) these may be described briefiy as follows:-

(a) Viscose can be made'as usual (or according to any known or approved formula) and to this can be added an organic material which is capable of reacting thereupon.

,(b) Alkali cellulose, made for example as in the usualmanner of. producing viscose (or in any known or approved manner), is treated with an organic material capable of reacting on the cel- .35 lulose content thereof with substitution of an organic radical in place of a hydroxyl hydrogen atom of the cellulose, after which the product is treated with carbon bisulphide, and the xanthated, product is dissolved in water in .the pres- 40 ence of alkali.

.These methods are described in detail in several of my other cases, as follows:

(a) As described and claimed in Ser. No. 435,-

649 filed March 13, 1930, to viscose there is added alpha dichlorhydrine, the amount of which may be equalto 10% to 40% of theweight of the cellulose used in making the viscose. Instead of adichlorohydrine, ,B-dichlorohydrine, epichlorohydrine, ethylene chlorohydrine, glycerine. mono- ,50 chlorohydrines, or another halogen derivative of a polyhydric alcohol, suchas pinacone chlorohydrine (tetramethyl-ethylene chlorohydrine),

mannite chlorohydrine, erythrite chlorohydrine or dichlorohydrine, pentaerythrite chlorohydrine,

,66. mannitane chlorohydrine, dulcitan monochlorohydrine, divinyl-ethylene glycol chlorohydrine, 'phenyl. propanol chlorohydrine, naphthyl propanol chlorohydrine, 4-methoxy naphthyl propanol chlorohydrine, and the like, as well as the analogous bromine derivatives.

The halogen derivative selected is added tothe viscose and well mixed therewith, and the soformed solution (optionally after suitable ripening) is converted into the proper shape and is treated with the plasticizing bath, or witha 00- 10 agulating bath and then with a plasticizing bath.

The artificial materials can be desulphurized with NazS solution, or equivalent, preferably with a warm or hot solution containing at least 5% of Na2S.9H2O, this step being claimed in my co- 15 pending application Ser. No. 464,426, filed June 27, 1930 In my copending application Ser. No. 464,427, filed June 2'7, 1930, I have described and claimed a modification of the above process, in which ingo stead of the halogen derivatives of polyhydric alcohols, trithiocarbonic acid esters of alcohols, and particularly such esters of polyhydric alcohols (e. g. glycols, glycerine, etc.) are employed for reacting on the viscose. 25

In my copending application 597,640 filed March 8, 1932, I have described a furthermodification, according to which cellulose xanthate (preferably in the form of viscose) is treated with one or more organic compounds of the type con- 30 taining a polyvalent aliphatic organic radical,to at least one carbon atom of which sulphur is'attached, and to at least oneother atom of which a halogen (e. g. chlorine or bromine) is attached, and which organic compounds, may or may, not 35 also contain oneor more hydroxyl groups. Such organic compounds can be made, for example by reacting on a dichlorohydrine with a solution containing an amount of NazS or NaHS less than the stoichiometrically equivalent of the halo- 40 gen element (chlorine) in the dihalogenhydrine (e. g. dichlorohydrine) This process and product are claimed in Ser. No. 597,641.

In another copending application Ser. No. 618,801 filed June 22, 1932, I have described and '45 claimed a further modification of the above process in which cellulose xanthate is treated with one or more organic compounds which contain an aliphatic polyvalent nucleus, to at least one carbon atom of which is attached a halogen element, (e. g. chlorine), to another of which is attached nitrogen such as an NHz group or NH group, and to another of which is attached oxygen such as a hydroxyl group. Such compounds can be prepared by acting on a dihalogen hydrine,

such as dichlorohydrine, with ammonia, preferably at belowC., and preferably disssolved in alcohol, this process and product being claimed in my copending application Ser. No. 618,800 of June 22, 1932.

somewhat analogous manner, then xanthating.

by treatment with CS2 and then dissolving the xanthated product in Water and a caustic alkali. Examples of these methods, aregiven in certain of my other cases as now to be mentioned.

In my application 435 6347, filed March 1930;

(now Patent 1,858,097) I have described and claimed a process in which to alkali cellulose (say a soda cellulose containing 1000 parts of air-dry cellulose and 2400 parts of NaOH solution of 18% strength) is'added 100 parts (or 100'to 300 parts 'i-nsome cases) of u-monochlorhydrine, then the mass is either xanthated with 600 parts of CS2, the excess of the latter blown ofi and the minthated product can be dissolved in causticalkali solution, or dissolved in caustic alkali solution and the'reafter xanthated in-solution. In place of the a-mon'ochlorhydrine, equivalents can be used as stated under 435,'649, above.

-In Ser. No. 435,648 I have descriibed and {claimed the making of artificial materials by treating suchisolutionsof xanthates of oxy-organo cellulose compounds as are produced under Patent 1,858,097, by treating the same, in a "-s'hapedcondition with a plasticizing agent, e. g.

H2804 of 35%, preferably 45% or stronger, or

other mineral acid of similar strength. Or, in -placeof this latter treatment, I can first introdues the shaped xanthate solution into adilute acid having merely a coagulating action thereon,

- ar'id'then (if desired) treat the freshly coagulated material with an acid solution having a plasti- "o'i'zirig action thereon, such as H2804 of 35% and preferably 45% or stronger.

In ser. No. 521,017 filed March '7, 1931, I have described and claimedthe making of artificial 'materials (including threads) by a process which diiiers'fromthe preceding by thetreatment of the alkali cellulose with an etherifying agent (an *alkylating-agent, an-aralkylating agentor a halo- "gen fa'tty acid or salt thereof), thenxanthating the thus obtained product in one of the manners described above in connection with Ser. No. 435,647, dissolving in caustic alkali and water,

shaping the solution of the Xanthate, coagulating andplasticizing the product, as described above.

In my'Patent 1,910,440, May 23, 1933, I have'described and claimed an analogous process in which cellulose, in the presence of an alkali, is reacted upon by acyclic ether of the type ethylene oxide, the product xanthated, dissolved in alkali solution, and coagulated and 'plasticized.

Many other organic substances can likewise react with the alkali cellulose, the reaction product xanthated and the xanthate solution shaped, co-

agulatedand (optionally) plasticized. Inmy co-' pending case 556,719 of August 12, 1931, I have described the employment of the following, for

thatpurpose, the following list:

.Di-ha'logen paraifines, for example compounds of the type'of-ethylene chloride or -tri-methylene chloride (which maybe regarded as halogen hydracidesters of dihydric paraiiinalcoholmgly- -cols') or: of thetype of methylene chloride (which may be regarded as neutral halogen hydracid esters of glycols wtih two hydroxyl groups attached to one and the same carbon atom). Poly-halogen paraflins. 1 1 Halogen olefins (halogen substitution products of unsaturated hydrocarbons).

Halogen derivatives of ethers of mono-hydric alcohols. 7 p g Halogen derivatives or aldehydesor ketones.

.Sulphochlorides of tertiary amines, such as, for example, the sulphochloride of dimethyl-aniline.

Halogen derivatives of higher fatty acids having at least '6 carbon atoms.

Halogen 'derivativeso'f olefine mono-carboxylic acids. I .1

Halogen alkylamines or halogen aralkylamines. Halogen derivatives of oxy-acids, for example p-di-chlo'ro lactic acid or p-tri-chloro-lactic acid. Halogen derivatives of keto-carboxylic acids. Halogen derivatives of nitro-methane, such as chloro-picr-in.

'Urea halides, alkyl urea ams, araixynum halides and ar yl-ure'a halides.

'Tri-thiocarbonic acid esters. 1

Halogen derivatives (ifcyanogen, such as cyam ogen halides 'or cyanuric halides '(tricya'no'gen halides). I I s Halogen derivatives of"di-uarboxylic acids, as halogen succinic a'c-id- I Organic acidesters and inorganic acid -es'ters of dior polyhydricsalcohols (other-thanihalegen hydraci'd-esters). I I I Some halogen derivatives o'f hydrocarbons ot the type "Gillian-+2, forexampie trimltltrrohydrin (l'z2z3- trichloropropene). I i

Sulphochloridesof hydrocarbons,such as orflmor paratoluene sulphochlo'ride, naphthalene sulpho-chloride. i Halogen -derivatives of l'ialogenated allkyl'phenyl ethers, such as -b'enzoyl'ated 'chloroanisol.

Acideste'i's or phenols, for example phenyl carbonate-or phenyl-ethylcarbonate.

' Ac'id halides, for example benwy'lhatidespmalonyl halides, diethyl malonyl halides.

-Halogen derivatives of -aromatic mono car-s acids, for exa'mple phenyl halogen lactic acid 0 phenyl halogen oxy-propionic acid'. I

Phenyl-acetylene. Halogen derivatives of I ole'flne-benzdls. Halogen derivatives or phenyl-olefine alcdliols or oxy-phenyl olefine alcohols.

Halogen clerivatives of pseudophe'nols;methylene quinones 'andouinols, -for example ortho-oxymesityl chloride or piperonyl-chloride.

Sulphochlorides of :phenyl-mon'o-oxy-oarbox- 'ylic acids, such as-salicylicacid or-cresotinic aeid and chloroor I nitro-subs'titution :productskthe'rel-lalogen derivatives 6f -'condsensed Lniiolei, for example a naphthalene mono-halides -or "halogenated 'naphtha-lenes.

Halogen derivatives of hydro-naphthalene compounds,v for example di-hydro-naphthalene- 'di-bromide or tetra hydroanaphthalene-glycol- -'-chlorhydrin.- s 1 1 Halogen derivatives iof h'et'erocylic compounds having one nitrogen atom in the ring, for example halogen derivatives of pyridine or-of its homologues, or halogen derivativesof quinoline or of example quinoline or pyridine.

In my. copending application 618,802," of 'June 222, 1932, I have described and claimed the'production of artificial materials from a xanthated "solution which has been prepared by acting on alkali cellulose with-an organic .material which contains hydroxyl attached to at least one carbon atom', and contains a halogen element attached to at least one other of the carbon atoms thereof, and at least one sulphur group (e. g. -SH) attached to still another of the carbon atoms thereof, and the said compound of alkali cellulose then xanthated by CS2, and dissolved.

Also in said application 618,802, there is de scribed the treatment of viscose with a compound of a polyvalent organic radical containing at least one nitrogen atom attached to a carbon atom, at least one oxygen atom attached to a carbon atom and at least one acid residue (preferably a halogen atom) attached to a carbon atom (the three being preferably attached to different carbon atoms. Such products can be made by reacting on a dichlorhydrine with ammonia, at a temperature preferably below 100 C.

In all of the above cases, it isto be understood that the solution of a xanthate of an oxy-organo cellulose compound is, after being formed into the desired shape (e. g. into the shape of l a thread-like stream) treated for being coagulated and plasticized, whereby products (e. g. threads) of high dry and wet tenacity, and high (or at least moderate) extensibility (i. e. extensibility not below about 7-9% and in some cases substantially higher) are produced. But the present invention is not limited to the treatment of products which have been so plasticized.

It will be understood that in many instances, it is entirely feasible to include both the treatment of the alkali cellulose with the organic reacting agents above described, and also the treatment of the xanthate (viscose) therewith, or in other words to add some of the organic reacting agent (one or a mixture of several) to the alkali cellulose, and to add some more of the same or a different reacting agent (one or a mixture of several) after the xanthation step (and optionally 1 after the dissolving step).

The said organic reagent, Whether added at one or both of the stages of the process indicated, may be insufficient to modify all of the cellulose present in the final xanthate solution, so that in such cases the final solution from which the artificial materials are to be regenerated, will contain some unmodified cellulose xanthate along with one or more xanthates of oxy-organo cellulose compound, whereby upon regeneration there is produced a mixture of cellulose with an oxy-organo derivative of cellulose.

I have now found it is sometimes difiicult to purify the artificial materials (including artificial threads) produced as described above, from such xanthates of oxy-organo cellulose compounds, or mixtures thereof with viscose, without impairing their extensibility and in some cases also their tensile strength and feel, by any methods heretofore known. The present invention involves a process, one object of which is to accomplish such purification without such injuries to the said invention which, however,

products. Andthe present invention also includes asimilar treatment ofartifi'cial materials produced by coagulating (and optionally plasticizing) ordinary viscose.

The present invention is based on the observa- -tion that well purified products namely artificial I materials such as artificial threads, having excellent dyeing and other properties are obtained when artificial materials prepared from the xanthatesolutions made by the above methods (or 1 any of them), are. treatedwith a warm. or hot alkali sulphide solution containing caustic alkali.

Thefollowing examples illustrate the present is in no way limited to these examples: y I m Example 1 A dry or Wet skein ofartificial silk produced according to one of the processes described above is treated by immersion, or spraying, or by any other method known in the desulphurizing art, with an aqueous solution of NazS.9H2O of 10 per cent. strength, and which contains to 7 per cent.

of caustic soda,- at 100 C. for to minutes. After that time, the skein is removed from the sodium sulphide plus caustic soda solution, washed with hot water, then with cold water after having been soured, if desired, with dilute sulphuric acid (for example, of 10 per cent. strength), thoroughly washed and dried.

Example 2 The process is conducted as in Example 1, but with the difference that the solution contains 30 per cent. of NazSBHzO and 5 to'7 per cent. of caustic soda.

Example 3 The process is conducted as in Example 1, but with the difference that the solution contains 58 per cent. of Na2S.9H2O and 5 to 7 per cent. of caustic soda.

Example 4 The process is conducted as in any one of Examples 1 to 3, but with the exception that the solution contains only 3 to 4 per cent. of caustic soda.

Example 5 Mode of procedure as in any one of the Examples 1 to 4, but with the difference that the desulphurizing treatment is conducted at 5 0 to 60 C.

The expression cellulosic body used in the claims is intended to include cellulose, cellulose conversion products and cellulose derivatives accessible to xanthation.

The expression cellulose used in the description and. claims means, wherever the context permits, cellulose and its near conversion products,

such as cellulose hydrate, hydrocellulose or 3% of iNaOH, .suchnsolutionbeing at a temperature of at least 50 C.., until said colored substances fare sufliciently removed.

2. A process as claimed inaclaim -1, iwherein the artificial 2 structures are subjected, during manu- .facture, toqa plasticizing treatment, in an acid having "a. :strength. equal to that of sulphuric acid ofat least'about 35%.

3. .A'process .as claimed in claim 1', .Whereinthe xanthalte of :oxy-organo compoundofcellulose is :a xanthate-of a cellulose ether.

:4. :A process as claimed in claim 1, wherein the alkali sulphide .solution contains alkali metalsul- :phide equivalent to not less thanBO per cent. of

crystallized sodium sulphide. 1

*4 wapoaarm' '5. vAprocess.as'claimed iniclaim 51, wherelnlthe alkali szflphide solution contains. not less than 15 per Y cent. of caustic-alkali (calculated as caustic soda).

6. A process as claimed in :1, wherein the :1 5 treatment is conducted at atempcrature noteubleast about 58% NazSBHzO and containing caustic alkali equivalent to at least"about l:5% NaOH, atatemperatur'e of about 100C.

LEON ELILIENFEIIJDQ :15 

